Manufacture of sulphated and phosphated oils



Patented Dec. 30, 1941 nanurac'ruaa or smna'ran m PHOSPHATED OILS Ralph E. Porter, East Orange, N. 1., assignor to National Oil Products Company,

N. L, a co 'lwtation of New Jersey No Drawing. Application September. 13, 1939,

Serial No. 294,627

2o Claims. (01. 260-400) This invention relates to oils for treatingfibrous materials such as textiles and leather, more particularly to sulphated oils and to a process for preparing sulphated oils containing substantially no undesirable sludges.

In. the course of the manufacture of sulphated fatty oils, the reaction ingredients come in contact with iron, leadand other metallic equipment so that the finished oils generally become contaminatedto some extent with these metallic substances. Such contamination, particularly that produced by iron and lead, causes the formation in the sulphated oils of sludgy precipitates having white, gray, brown or reddish-brown colors, and which detract from the appearance of the oils, in many cases giving the consumer an impression of inferior quality. The

may produce stains and blotches on leather and textile materials treated therewith so that the commercial value of the oils is somewhat disuccessful method of preventing the formation of sludges has been proposed; the sludges were the above group is added to the partially neutralized sulphated mass from which the acids and salts have been permitted to settle, i. e., just prior to finishing the oil, since I have found that the most satisfactory results are obtainable ,thereby. However, the hydroxy carboxylic proves the action of these compounds. My-

invention not only permits the production of sulphated fatty oils containing no objectionable Ill 7 presence of these sludges in sulphated oils also either permitted to remain in the oils, if their quantity was not toogreat, or were removed by filtration, which ordinarily was a long and expensive operation.

It is the object of this invention to provide a process for the preparation of sulphated fatty oils containing substantially no iron or other metallic sludges,

I have made the surprising discovery that the incorporation of a relatively small amount of a compound selected from the group consisting of hydroxy carboxylic acids, derivatives thereof having a free hydroxyl group and at least one free .carboxyl group, and water-soluble salts of these compounds, in a sulphated fatty oil prevents the formation of iron, lead and other mearate from the partially neutralized mass, re-,

moving said aqueous layer, and then finishing the sulphated product by adjusting its pH and its water content to the desired values. In accordance with the preferred embodiment of my invention a relatively small amount of a hydroxy carboxylic acid compound selected from precipitates due to the presence of metallic soaps, but also sulphated .oils having much lighter colors than heretofore obtainable by the ordinary methods of sulphation may be obtained. In the interest of brevitythe term hydroxy carboxylic acid compound" is employed throughout the specification to denote a compound selected from the group consisting'of hydroxy carboxylic acids, derivatives thereof having a free hydroxyl group and at least one free carboxyl group, and watersoluble salts of these compounds.

My invention is applicable to the treatment of any sulphated fatty oil; these oils are more commonly known in the trade as sulphonated oils and include products such as sulphated sperm oil, sulphated oleic acid, sulphated codv oil, sulphated olive oil, sulphated neats-foot oil,

sulphated teaseed oil, and sulphated rice bnan' oil. In general it may be said that any sulphated fatty oil which may be employed for treating fibrous materials such as leather or textiles may advantageously be prepared. in accordance with my invention. When operating in accordance withthe preferred embodiment of my invention, a raw fatty oil may be treated in the ordinary manner with a sulphating agent such as concentrated sulphuric acid, oleum, or chlorsulphonic acid, the sulphated mass washed and the washed mass partially neutralized toa pH value between about 3.5 and about 5 and permitted to stand until the aqueous layer containing inorganic salts and acids separates substantially completely. To the partially "neutralized mass thus prepared may then, in accordance with my invention, be added a relatively small amount of a hydroxy carboxylic acid compound. The amount of the hydroxy carboxylic acid compound added to the partially neutralized mass may .vary widely, but preferably should be such as to produce a finished sulphated oil containing between about 0.1% and about 1%, e. g., about 0.2% of the compound. I prefer to employ tartaric acid in the practice of my invention on account of the excellent results obtained with this compound. However, other hydroxy carboxylic acids'such as lactic acid, hydroxy stearic acid, gluconic acid, malic acid and salicylic acid may be employed, as well as derivatives thereof having a free hydroxyl group and at least one free carboxyl group such as the monoethanolamide of tartaric acid or the ur'eide of citric acid. Furthermore watersoluble salts of these acids or their above-mentioned'derivat'ives such as the alkali and ammonium salts may also be used; for example, I have found excellent results may be obtained by using sodium tartrate, sodium potassium tartrate, or sodium lactate. The hydroxy carboxylic acid compound is preferably added in relatively pure form but solutions thereof may be added if convenient. The addition my be accomplished in any desired manner; for example, the compoundmay be added to the oil and agitated until solution is substantially complete. a

I have also found that it'is preferable to incorporate a relatively small amount of a reducing agent in the partially neutralized mass along with the hydroxycarboxylic acid compound, since in many cases clearer and more stable sulphated oils are obtained thereby than may be produced by the use of a hydroxy carboxylic acid compound The partially neutralized mass treated in ac- -cordance with my invention may be finished 'by adjusting its moisture content and pH value to the desired points; such a product, I have found, contains no precipitated metallic soaps and may be permitted to stand indefinitely without metal lic soaps settling out. Hence the products of my invention are eminently suitable for treating fibrous materials such as leather and textiles.

My invention may also be carried out by treating sulphated fatty oils which have already been finished; thus, for example, a finished sulphated oil having a pH value of about 6 and containing about 25% moisture and which contains sludgy precipitates due to the presence of iron or othermetallic soaps may be cleared bythe addition of a small amount of a hydroxy carboxylic .acid compound and preferably also a reducing agent. In some cases I have. found it desirable to lower the pH value of the finished oil in order to obtain the maximum clearing effect. Occasionally treatment of finished sulphated oils in accordance with my invention causes clouding of the oil to take place; however, this clouding may be removed by readjusting the pH value of the finished oil to the desired point.

The following examples are illustrative of my' invention. Amounts are given in parts by weight. Example I 100 parts of sperm oil were cooled to a temperature cf about 10 C. and 30 parts of 98% sulphuric acid were added thereto. The mixture was then agitated for about two hours, the tem perature being maintained below 20 C. The reaction mass was washed with approximately four times its weight of an 8% sodium chloride solution, permitted to stand for from one to about two hours, and the aqueous layer which separated withdrawn. The washed mass was partially neutralized to a pH value of about 4 with soda and permitted to settle. for about 16 to 24 hours, at the end of which time the aqueous layer which separated was withdrawn. 0.3 part of tartaric acid was then added to the reaction mass with stirring. The oil was finished by adjusting its moisture contentto about 25% and its pH value to about 6. This oil contained no sludgy precipitates of any kind, although it was. prepared in standard plant equipment, including lead-lined iron kettles and iron pipes. The same oil when sulphated as above describedexcept that no tartaric acid was incorporated therein contained substantial amounts of undesirable sludges.

Example II 100 parts of oleic acid wc e cooled to a temperature of about 10 C. and 25 parts of 98% sulphuric acid were added'thereto. The mixture was stirred for about two hours, the temperature being maintained below 20 C. The reaction mass was then washed with approximately four times its weight of an 8% sodium chloride solution, the washed mass permitted to stand for from one to. two hours, and the aqueous layer which separated withdrawn. The washed mass was neutralized to a pH value of' about 4 and permitted to settle for about 16 hours, at the end of which time the aqueous layer which sepa-= rated was withdrawn. 0.3 part of sodium bisulphite and 0.9 part of 44% lactic acid were thenincorporated in the sulphated mass. The mass was finished by adjusting its moisture content to about 25% and its pH to about 6. The sulphated oil thus prepared contained no sludgy precipitates of any kind and remained stable even after prolonged standing, although it was prepared in standard plant equipment, including lead-lined iron kettles and iron pipes. The same oil when sulphated as above described except that no lactic acid and sodium bisulphite were incorporated therein contained substantial amounts of undesirable sludgy precipitates.

It will be evident from the above description 50 that the process of my invention constitutes a marked improvement in the manufacture of sulphated oils, since sulphated oils containing substantially no iron or other metallic sludges may always be obtained by the process of my invention, even though the pils contact iron, lead or other metallic equipment (during their manufacture. Furthermore I have found that sulphated oils prepared in accordance with my invention possess much lighter colors than similar oils prepared by the methods now knownto the art. My invention, therefore, will be of great value to those engaged in the manufacture of sulphated oils, particularly oils to be used in the treatment of fibrous -materials.

In view of the well known physical and chemical similarities existing between sulphated fatty oils and the corresponding phosphated fatty oils, my invention is also intended to cover the treat- 70 ment of phosphated fatty oils in the manner described above.

Since certain changes may be made in carrying out the above process without departing from the scope of the invention; it is intended that all '15 matter contained in the above description shall lim- 1. In the manufacture of an oil selected from the group consisting of sulphated and phosphated fatty oils, the step which comprises incorporating in the oil a relatively small amount of a compound selected from the group consisting of hydroxy carboxylic acids, derivatives thereof having a free hydroxyl group and at least one free carboxyl group, and water-solublesalts of these compounds.

2. In the manufacture of an oil selected from the group consisting of sulphated and phosphated fatty oil s,the step which comprises incorporating in the oil relatively small amounts of a compound selectedfrom thegroup consisting of hydroxy carboxylic acids, derivatives thereof having a free hydroxyl group and at least one free 10. In the manufacture of sulphated fatty oils, the step which comprises incorporating relatively small amounts of tartaric acid and sodium bisulphite in the 011 just prior to the finishing treatment.

11. A clear, stable oil selected from the group consisting of sulphated and phosphated fatty oils and containing a relativel small amount of a carboxyl group, and water-soluble salts of these compounds and a reducing agent.

3. In the manufacture of sulphated fatty oils,

the step which comprises incorporating in the oil just prior to the finishing treatment a relatively small amount of a compound. selected from the group consisting .of hydroxy carboxylic acids, derivatives thereof having a free hydroxyl group and at least one free carboxyl group, and watersoluble salts of these compounds.

4. In the manufacture of sulphated fatty oil s,

oil a sufllcient amount of a compound selected from the group consisting of hydroxy carboxylic acids, derivatives thereof having a free hydroxyl group and at least onefree carboxyl group, and water-soluble salts of these compounds, so that compound selected-from the group consisting of hydroxy .carboxylic acids, derivatives thereof having a free hydroxyl group and at least one free. carboxylgroup, and water-soluble salts of these compounds.

12. A clear, stable oil selected from the group consisting of sulphated and phosphated fatty oils and containing relatively small amounts of a compound selected from the group consisting of hydroxy carboxylic acids, derivatives thereof having a free hydroxyl grpup and at least one free carboxyl group, and water-soluble salts of these compounds and a reducing agent.

13. A clear, stable sulphated fatty oil containing between about 0.1% and about 1% of a. compound selected from the group consisting of hydroxy carboxylic acids, derivatives thereof having a free hydroxyl group and at least one free carboxyl group, and water-soluble saltsof these compounds.

r 14. A clear, stable sulphated fatty oil containing between about 0.1% and about 1% of a compound selected from the group consisting of hydroxy carboxylic acids,.derivatives thereof having a free hydroxyl group and at least one free carboxyl group, and water-soluble salts of these compounds and between about 0.1% and about a ingrelatively small amounts of tartaric acid and the finished oil contains between about 0.1% and about 1% of said compound.

6. In the manufacture of sulphated fatty oils,

the step which comprises incorporating in the oil sumcient amounts of a compound selected from the group consisting of hydroxy carboxylic acids,

derivatives thereof having a free hydroxyl group and at least one free carborwl group, and watersoluble' salts of these compounds and a reducing agent, so that the finished oil contains between about 0.1% and about 1% of the acid and of the v mass, permitting the partially neutralized mass 9. In the manufacture of sulphated fatty oils, Y

the step which comprises incorporating a relatively small amount of lactic acid in the prior to the. finishing treatment.

oil'just 7 alkalibisulphite, and

sodium bisulphite.

19. A process for the preparation of a sulphated oil which comprises treating afatty oil with a sulphating agent, washing the mass with an aqueous medium, partially neutralizing the mass, permitting the partially neutralized mass to settle, removing the aqueous material which separates therefrom, adding to the mass a relatively small amount of a compound selected from the group consisting of hydroxy carboxylic'acids, derivatives thereof having a free hydroxyl group and at least one free-carbonyl group, and watersoluble salts of these compounds and finishing.

20. A process for the preparationof a sulphated oil which comprises treating a fatty oil with a sulphating agent, washing the s with an aqueous medium, partiallyneutralizing the to settle and removing the aqueous material which separates therefrom, adding to the mass relatively small amounts of a compound selected from the group consisting of hydroxy carboxylic acids, derivatives thereof having a free hydroxyl group and at least one free carboxyl group, and

water-soluble salts of these compounds and an finishing- RALPH E. PORTER. 

